Hydroxybenzensulfonyl halide production

ABSTRACT

The conversion of hydroxybenzenesulfonates to the corresponding hydroxybenzenesulfonyl halides by contacting with a thionyl halide, a phosphorus oxyhalide or a carbonyl halide in the presence of catalytic amounts of selected organic phosphorus compound.

United States Patent nan, Jr. et al.

[ June 27, 1972 HYDROXYBE NZENSULFONYL HALIDE PRODUCTION Inventors:Harold Wayne Hill, Jr.; Robert W. Campbell, both of Bartlesville, Okla.

Assignee: Phillips Petroleum Company Filed: March 1 1, 1969 Appl. No.:806,281

U.S.Cl. ..260/543 R int. Cl ...C07c 143/70 Field of Search ..260/543 RReferences Cited OTHER PUBLICATIONS Fieser et al., Reagents for Org.Synth., p. 1247, Q 262E5.

Primary ExaminerLorraine A. Weinberger Assistant Examiner-E. Jane SkellyAttorneyYoung and Quigg [5 7] ABSTRACT The conversion ofhydroxybenzenesulfonates to the cor- 7 Claims, No DrawingsHYDROXYBENZENSULFONYL I-IALIDE PRODUCTION BACKGROUND OF THE INVENTIONThis invention relates to a process for the preparation ofhydroxybenzenesulfonyl halides. In accordance with another aspect, thisinvention relates to the conversion of hydrox ybenzenesulfonates to thecorresponding hydroxybenzenesulfonyl halides in the presence of selectedorganic phosphorus catalysts.

I-Iydroxybenzenesulfonyl halides, particularlypara-hydroxybenzenesulfonyl halides, are homoreactive by virtue of thefact that the two functional groups, the sulfonyl halide and thehydroxyl groups, are highly reactive and readily combined; the order ofreactivity being lowest for the fluorine derivative and increasing to amaximum for the iodine analog. A relatively stable sulfonyl halide,p-hydroxybenzenesulfonyl fluoride, has been prepared as described bySteinkopf, et al. J. prakt. Chem., 117, 1-82 (1927). However, attemptsto prepare hydroxybenzenesulfonyl chloride, bromide, or iodide have beenunsuccessful due to the high reactivity of the thionyl halide,phosphorus oxyhalide, or carbonyl halide with the hydroxyl group.

In accordance with the invention, we have found that novelhydroxybenzenesulfonyl halides, not heretofore prepared or isolated, canbe prepared and recovered as essentially pure compounds by the uniqueprocess of this invention wherein hydroxybenezenesulfonyl halides areprepared using selected organic phosphorus catalysts.

Accordingly, it is an object of this invention to provide novel, usefulhydroxybenzenesulfonyl halides.

It is another object of this invention to provide novelhydroxybenzenesulfonyl chlorides, bromides and iodides.

It is yet another object of this invention to provide a method forproducing hydroxybenzenesulfonyl halides.

It is yet another object of this invention to provide a method forproducing para-hydroxybenzenesulfonyl halides.

Other objects, aspects as well as the several advantages of theinvention will be apparent to those skilled in the art upon reading thespecification and the appended claims.

SUMMARY OF THE INVENTION In accordance with the invention,hydroxybenzenesulfonates are converted to the correspondinghydroxybenzenesulfonyl halides by contacting thehydroxybenzenesulfonates with a halogen donor, preferably a thionylhalide, phosphorus oxyhalide or carbonyl halide, in the presence of acatalytic amount of a promoter comprising certain organic phosphoruscatalysts.

In carrying out the invention it is presently preferred that the cationof the sulfonate be an alkali metal, more particularly sodium,potassium, lithium, rubidium and cesium. The halogen group of theresulting sulfonyl halide will, of course, be the same as that in thehalogen donor, i.e., the thionyl halide, phosphorus oxyhalide orcarbonYl halide. Due to the extremely high reactivity of the iodinederivative of the hydroxybenzenesulfonates, although all of the halogenanalogs can be prepared by this procedure, we have found that thegreatest degree of success in the preparation of these compounds isaccomplished by the use of fluorine, chlorine and bromine donors, i.e.,thionyl and carbonyl fluoride, chlorides and bromides and phosphorusoxychloride, oxyfluoride and oxybromide in the production of thecorresponding sulfonyl fluorides, chlorides and bromides.

The selected organic phosphorus catalysts of the invention which can beemployed are selected tri-substituted phosphoric acid, phosphine, orphosphine oxide derivatives which can be represented by the formulas:

wherein R is alkyl, cycloalkyl, aryl, or combinations thereof, such asalkaryl, or aralkyl, having in the range of about 1 to 8 carbon atoms;and wherein R is R, RO, or (R)2-N. Such compounds includehexahydrocarbyl phosphoric triamides, trihydrocarbyl phosphates,trihydrocarbylphosphines, and trihydrocarbylphosphine oxides.

Representative examples of specific organic phosphorus compounds thatcan be employed as catalysts according to the invention include:

triphenylphosphine triphenylphosphine oxide hexarnethyl phosphorictriamide trimethylphosphine trioctylphosphine methyldioctylphosphinemethyldi( 2-methylbutyl )phosphine tricyclopentylphosphinetricyclooctylphosphine tribenzylphosphine tri( 2-phenylethyl)phosphinetri( 3-ethylphenyl )phosphine tri( Z-methylphenyl )phosphine tri(2-methylcyclopentyl )phosphine tri( 4-ethylcyclohexyl)phosphine tri(cyclopentylmethyl)phosphine tri( 2-cyclohexylethyl)phosphinetrimethylphosphine oxide trioctylphosphine oxide methyldihexylphosphineoxide methyldi( 3-ethylpentyl)phosphine oxide tricyclopentylphosphineoxide tricyclootylphosphine oxide tribenzylphosphine oxide tri(2-phenylethyl)-phosphine oxide tri( 3-ethylphenyl )phosphine oxide tri(2-methylphenyl)phosphine oxide tri( 2-methylcyclopentyl) oxidetri(4-ethylcyclohexyl)phosphine oxide tri( cyclopentylmethyl)phosphineoxide tri( Z-cyclohexylethyl)phosphine oxide hexaoctyl phosphorictriamide hexacyclopentyl phosphoric triamide hexacyclooctyl phosphorictriamide hexabenzyl phosphoric triamide hexa( 2-phenylethyl)phosphorictriamide hexa( 3-ethylphenyl)phosphoric triamide hexa(2-methylphenyl)phosphoric triamide hexa( Z-methylcyclopentyl )phosphorictriamide hexa( 4-ethylcyclohexyl )phosphoric triamide hexa(cyclopentylmethyl )phosphoric triamide hexa(2-cyclohexylethyl)phosphoric triamide trimethyl phosphate trioctylphosphate methyldioctyl phosphate ethyldi( Z-methylbutyl )phosphatetricyclopentyl phosphate tricyclootyl phosphate tribenzyl phosphate tri(2-pentylethyl)phosphate tri( 3-ethylphenyl )phosphate tri(4-methylphenyl)phosphate tri( 2-methylcyclopentyl )phosphate tri(3-ethylcyclohexyl )phosphate tri( cyclopentylmethyl)phosphate tri(2-cyclohexylethyl)phosphate.

The conversion of hydroxybenzenesulfonates to hydroxybenzenesulfonylhalides according to the invention can be represented by the followingreaction:

wherein M is Na, K, Li, Rb, or Cs; wherein X is Cl, F, or Br; whereinone and only one Y per molecule in -Ol-l; wherein all other Ys permolecule are H or alkyl, cycloalkyl, aryl, or combinations thereof, suchas alkaryl, or aralkyl, having in the range of about one to eight carbonatoms.

Representative examples of hydroxybenzenesulfonates which can beemployed include:

sodium 4-hydroxybenzenesulfonate potassium B-hydroxybenzenesulfonatelithium 2-hydroxybenzenesulfonate rubidium4-hydroxy-3S-dimethylbenzenesulfonate cesium4-hydroxy2,6-dibenzylbenzenesulfonate potassium2-hydroxy-4-cyclooctylbenzenesulfonate potassiumZ-methyl-3-phenyl-4-hydroxy-5-cyclopentyl-6-( 2CYCLOHEXYLETHYL)benzenesulfonate sodium 4-hydroxy-2,6-di(3-methylpentylbenzenesulfonate sodium4-hydroxy-2,6-diethylbenzenesulfonate lithium4-hydroXy-2,6-dioctyl-3,5-di(3-ethylphenyl)- benzenesulfonate sodium 3hydroxy-5-(4-ethyl cyclohexyl)benzenesulfonate sodium2-hydroxy-o-phenylbenzenesulfonate potassium4-hydroxy-2,6-diethylbenzenesulfonate potassium3-hydroxy-5-cyclopentylbenzenesulfonate sodium 4-hydroxy-2,6-di(2-methylbutyl)benzenesulfonate Catalytic amounts of the catalysts of theclass described above include those amounts of those catalystssufiicient to catalyze the desired conversion of sulfonate to sulfonylhalide within a reasonable period of time, while not exceedingconcentrations above which homoreactivity of the hydroxybenzenesulfonylhalide products is substantially accelerated. Amounts of catalysts notexceeding about 25 parts by weight of catalyst per 100 parts by weightof hydroxybenzenesulfonate are normally suitable. in general, amounts ofthe range of about one to 15 parts of catalyst per 100 parts ofhydroxybenzenesulfonate are most suitable. Of course, the optimum amountof the particular catalyst employed with the particularhydroxybenzenesulfonate under the particular reaction conditionsemployed can readily be determined by one skilled in the art, within theranges defined Reaction temperatures in the range of from about C. toabout 100 C. are usually employed in this process although higher andlower temperatures can be employed. We have found, however, thattemperatures within the range of about 50 C. to about 70 C. provide themost advantageous results under most circumstances. Thoughsuperatmospheric or subatmospheric pressures can be employed, the use ofatmospheric or slightly higher pressures is generally preferred forconvenience and prevention of reactor contamination.

crystalline product into a solvent such as benzene at a convenienttemperature, say at about room temperature, cooling to solidify thesolution, and then adding a second solvent (for example, hexane) that issubstantially not a solvent for a hydroxybenzenesulfonyl halide butwhich is miscible in the solvent employed previously. The second solventand the frozen mixture are allowed to equilibrate resulting in theseparation of p-hydroxybenzenesulfonyl halide. Crystalline material ofhigh purity has been obtained, using the above process, even whenstarting with crude oil-like products.

The hydroxybenzenesulfonyl halide products of the instant invention canbe recovered by employing the crystallization process which is disclosedin copending application having Ser. No. 806,280, filed Mar. 1 l, 1969.In effect, that process comprises dissolving a crudehydroxybenzenesulfonyl halide The hydroxybenzenesulfonyl halides thatare produced according to the process of this invention are useful asprecursors to valuable polymers having regular repeating unitscharacterized by the formula l /rhll L UH EXAMPLE I At C. to a stirredreactor were charged 9.8 g of sodium p-hydroxybenzenesulfonate and amixture comprised of 30 g of thionyl chloride and amounts of catalyst asare presented in the following table, Table I. The reactor contents werestirred at 60 C. for 3% hours, and were then slowly poured over icewater. An oily layer formed on the bottom and was taken up indichloromethane. Further washing with water and dichloromethane waseffected. The dichloromethane solution was dried with magnesium sulfateand the solution was stripped of volatiles. Product, in the yields givenin Table I, below, was recovered in each run. The products wereidentified by infrared analysis to be composed ofp-hydroxybenzenesulfonyl chloride.

This example demonstrates that hydroxybenzenesulfonyl halides are formedfrom hydroxybenzenesulfonates according to the process of this inventionemploying the catalytic com- The degree of conversion will, of course,depend on the du- 50 pounds of this invention.

TABLE I Quantity of Run catalyst Yield No. Catalyst (g-) (8-) 1Triphenylphosphine 0.29 1. 34

2 Triphenylphosphine oxide @)PO 0.29 1.19

3 Hexarnethyl phosphoric triamlde. [(CHahNkPO 0. 29 0. 51 4 d0[(CH3)2N]3PO 0. 69 1636 0 5 None (control) ration for which the reactionis continued. Generally, reaction times within the range of about 1minute to 20 hours are most suitable, preferably 1 to 10 hours areemployed. Conventional equipment and conventional techniques can beemployed to effect the desired conversion. Reaction can be carried outand equipment operated on continuous, semi-continuous or batchprinciples and techniques.

Mole ratios of the hydroxybenzenesulfonate to halogen donor areordinarily in the range of 110.5 to 1:50, and are preferably in therange of 1:2 to 1:10.

EXAMPLE II A stirred reactor maintained under N was charged with 1.93 gof 4-hydroxybenzenesulfonyl chloride, 6 ml. of N- methylpyrrolidone, and4 ml. of dimethylacetamide. Upon lowering the temperature to 3 5 C, 1.5g of triethylamine was added. After 10 minutes reaction at -35 C, 200 mlof H 0 was added and the polymer was filtered from the mixture. Thepolymer was washed with water, methanol, water, methanol, and repeatedlywith hot acetone (50 C). The washed polymer was dried at 70 C for 16hours to yield 1.05 g of dried polymer. The inherent viscosity of thepolymer in LiCl-N- methylpyrrolidone was 0.60. A sample of this polymerwas molded at 280 C, 1,500 psig for 30 seconds and quenched in coldwater. Film had a thickness of 7 mils and a tensile strength of 6,885psig with an elongation of 2 percent. The film was tough and clear.

We claim:

1. A process for producing hydroxybenzenesulfonyl halides whichcomprises reacting (a) a hydroxybenzenesulfonate, wherein the cation ofthe sulfonate is an alkali metal, with (b) a member from the groupconsisting of thionyl halides, carbonyl halides and phosphorusoxyhalides, in the presence of (c) an organo-phosphorus compound of theformula wherein R is alkyl, cycloalkyl, aryl, or combinations thereof,such as alkaryl or aralkyl, having in the range of about one to eightcarbon atoms; and wherein R is R, R-O-, or (R) -N-, wherein the amountof said organo-phosphorus compound is sufficient to catalyze theconversion of said hydroxybenzenesulfonate to saidhydroxybenzenesulfonyl halide but does not exceed about 25 parts byweight of said organophosphorus compound per parts by weight of saidhydroxybenzenesulfonate.

2. A process according to claim 1 wherein the halides of (b) arechlorine, fluorine or bromine.

3. A process according to claim 1 wherein said hydroxybenzenesulfonylhalides are para-hydroxybenzenesulfonyl halides.

4. A process according to claim 1 wherein the amount of organicphosphorus compound present is an amount from one to 15 parts per 100parts of said hydroxybenzenesulfonate.

5. A process according to claim 1 wherein said contacting is effected bythe temperature in the range of about 0 C. to about 100 C.

6. A process according to claim 1 wherein (a) is' sodiumphydroxybenzenesulfonate and (b) is thionyl chloride and the productobtained is p-hydroxybenzenesulfonyl chloride.

7. A process according to claim 1 wherein (c) the organic phosphoruscatalyst is triphenylphosphine, triphenylphosphine oxide, or hexamethylphosphoric triamide.

2. A process according to claim 1 wherein the halides of (b) arechlorine, fluorine or bromine.
 3. A process according to claim 1 whereinsaid hydroxybenzenesulfonyl halides are para-hydroxybenzenesulfonylhalides.
 4. A process according to claim 1 wherein the amount of organicphosphorus compound present is an amount from one to 15 parts per 100parts of said hydroxybenzenesulfonate.
 5. A process according to claim 1wherein said contacting is effected by the temperature in the range ofabout 0* C. to about 100* C.
 6. A process according to claim 1 wherein(a) is sodium p-hydroxybenzenesulfonate and (b) is thionyl chloride andthe product obtained is p-hydroxybenzenesulfonyl chloride.
 7. A processaccording to claim 1 wherein (c) the organic phosphorus catalYst istriphenylphosphine, triphenylphosphine oxide, or hexamethyl phosphorictriamide.